Poly(oxyalkylene) modified phthalocyanine colorants

ABSTRACT

A colorant for natural or synthetic resinous or polymeric materials, having the formula: 
     
         A--[D--Z--SO.sub.2 --N(R.sub.2)--Y].sub.1-16 
    
     wherein; R 2  is selected from hydrogen, methyl, cyclohexyl, phenyl or Y; A is a nonionic metallophthalocyanine chromophore which can be substituted for example with halogen, alkyl, alkoxy, alkylthio, or aryloxy; Z is an arylene moiety; D is a linking group being or containing at least one of --O--, --S--, --SO 2  --, --N(R 3 )--, or --N(SO 2  R 4 )-- as the linking moiety, wherein R 4  is unsubstituted or substituted alkyl, cycloalkyl or aryl, and R 3  is R 4  or hydrogen; Y is a poly(oxyalkylene) moiety containing at least three monomeric units of the formula (--RO--) wherein each R is straight or branched alkylene of 1-4 carbons or mixtures thereof, up to about 20 mole percent of said monomeric units may be connected by one or more linking groups such as alkyleneoxy, --NH--, or --NHCONH--, and wherein Y can be terminated by hydrogen, or by or contain as branch substituents, 1-3 groups or moieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any of the above recited hydrocarbon groups, moieties or substituents may themselves be substituted with up to four substituents selected, for example, from alkyl, halogen, mercapto, alkoxycarbonyl, hydroxy, alkoxy, or the like; and wherein each aliphatic hydrocarbon portion or moiety of the groups, moieties or substituents recited above contains from 1-20 carbons.

This invention new colorant compositions, their manufacture and uses, and particularly concerns such compositions for the tinting or deeper coloring of natural and synthetic polymeric or resinous materials or substrates, especially polyurethales and other thermosetting resins and polyolefins, wherein the chemical structures of the colorants are readily tailored to meet, in exceptional manner, the physical and chemical requirements of the specific industrial application.

Some of the desired physical and chemical characteristics of such colorants in addition to having at least substantial tinctorial power, include one or more of excellent clarity and light fastness, high heat stability, crystal structure and shade immutability, availability as liquids or at least good resin compatibility at processing temperatures for easy blending with the substrate, easy clean-up from processing, homogeneity of dispersal in the substrate, non-nucleating propensity of the colorant, and resistance to migration, settling, streaking, plating, subliming, blooming and the like of the colorant from the substrate.

Other desirable colorant properties and also other problems often encountered with the use of pigment material are discussed in U.S. Pat. No. 4,284,729 the disclosure of which is incorporated herein by reference. In that patent which is principally concerned with coloring thermosetting or cross-linkable resins, it is disclosed that conventional organic dyes can be modified with poly(oxyalkylene) constituents which carry reactive groups for entering the colorant into the polymer chain, e.g., by condensation. This technique is indicated as providing a mechanism whereby highly efficient (high tinctorial power) conventional organic dyes can readily be incorporated, chemically, into the resin molecule such that the dyes become essentially nonmigratory. Similarly, in U.S. Pat. No. 4,640,690 the disclosure of which is incorporated herein by reference, it is taught to color thermoplastic resins with compounds which contain conventional types of organic dyes such as azo, anthraquinone, triarylmethane and methine, linked directly to a poly(oxyalkylene) moiety through a nitrogen, oxygen or sulfur atom or a carboxyl group.

It is noted that in these patents the methods for associating the poly(oxyalkylene) moieties with the chromophore are specific to the reactants. For example, in the preparation of azo containing colorants an aromatic amine is reacted with an alkylene oxide under basic conditions. Similarly, where the poly(oxyalkylene) is attached directly to an anthraquinone nucleus the method comprises reacting a hydroxy substituted anthraquinone with an amino group on a poly(oxyalkylene). Neither of these nor similar methods are useful in the present invention.

It has been found moreover, that the use of such conventional organic dye moieties in thermosetting substrates limits the utility of the product in, e.g., high temperature applications for which the substrate material may actually have been designed. This results from the inherent instability of the conventional organic dye moiety at the higher use or processing temperatures of the product substrate.

Also noted here are the copper phthalocyanine (CuPc) compounds of U.S. Pat. No. 4,634,555 which are solids in contrast to the great majority of the compounds of the present invention. The liquid colorants are quite easily blended uniformly with a variety of thermoplastic or thermosetting resins. In contrast, the solid prior art CuPc compositions would need to be converted into fine particles and then blended in conventional equipment which necessarily is time consuming and operator intensive, and incurs homogeneity problems, substantial power requirements, and great difficulty in handling and equipment clean-up.

Objects, therefore, of the present invention are to provide colorants, the physical and chemical properties of which are readily modifiable to adapt them for blending or incorporation into various polymeric substrates, especially in thermosetting resin materials, wherein the colorants exhibit one or more of the aforementioned characteristics of substantial tinctorial power, light fastness excellent clarity, high heat stability, crystal structure and shade immutability, availability as liquids for easy blending with the substrate; to give essentially complete homogeneity of colorant, easy clean-up from processing, non-nucleating propensity, and resistance; to migration, settling, streaking, plating, subliming, blooming and the like of the colorant from the substrate; to provide compositions comprising polymeric substrates, especially polyurethane foams, tinted or deeper colored with the present colorants; and to provide a highly efficient and non-complex process for the manufacture of the present colorants.

These and other objects hereinafter becoming evident have been attained in accordance with the present invention in which the colorant has the formula:

    A--[D--Z--SO.sub.2 --N(R.sub.2)--Y].sub.1-16

wherein; R₂ is selected from H or unsubstituted or substituted alkyl, cycloalkyl, aryl or Y; A is a nonionic metallophthalocyanine chromophore which can be substituted or unsubstituted; Z is a cyclic, unsaturated moiety hereinafter termed "arylene"; D is a linking group being or containing at least one of --O--, --S--, --SO₂ --, --N(R₃)--, or --N(SO₂ R₄)-- as the linking moiety, wherein R4 is unsubstituted or substituted alkyl, cycloaliphatic or aryl, and R₃ is R₄ or hydrogen; Y is a poly(oxyalkylene) moiety comprised of at least about 50 mole percent of monomeric units or mixture thereof of the formula (--RO--) wherein each R is substituted or unsubstituted straight or branched alkylene of 1-4 carbons or mixtures thereof; and wherein each aliphatic hydrocarbon portion or moiety of the groups, moieties or substituents recited above contains from 1-20 carbons.

In certain preferred embodiments:

(a) A is a nonionic metallophthalocyanine chromophore which can be substituted with 1-12 substitutents selected from halogen, alkyl, alkoxy, alkylthio, or aryloxy, or one to four --SO₂ N(R₂)--Y; Y is a poly(oxyalkylene) moiety comprised of at least three monomeric units or mixture thereof of the formula (--RO--) wherein, each R is straight or branched alkylene of 1-4 carbons or mixtures thereof, up to about 20 mole percent of said monomeric units may be connected by one or more linking groups selected from alkyleneoxy, aryleneoxy, alkylenedioxy, alkylenetrioxy, --N(R₅)--, or --N(R₂)CON(R₂)--, wherein each R₅ is selected from R₂ or --SO₂ --A, and wherein Y can be terminated by hydrogen, or by or contain as branch substituents, 1-3 groups or moieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any of the above recited hydrocarbon groups, moieties or substituents may themselves be substituted, for example, may contain up to four substituents selected from alkyl, halogen, alkoxycarbonyl, hydroxy, alkoxy, alkylenedioxy, aryloxy, alkoxyalkyl, aryloxyalkyl, mercapto, alkylthio, arylthio, --N(R₂)CO(R₂)(R₂), --N(R₂)(R₂), --N(R₂)SO₂ --A, --N(R₂)--acyl, --CON(R₂)(R₂), acyloxy or the like substituents which are known in the art; and wherein each aliphatic hydrocarbon portion or moiety of the groups, moieties or substituents recited above contains from 1-20, preferably 1-12 carbons.

(b) Y has an average molecular weight of from about 200 to about 1500;

(c) the chromophore A nucleus is unsubstituted;

(d) Y is terminated with a group selected from alkyl, aryl, acyl, alkoxyalkyl, mono- or dihydroxyalkyl, acyloxyalkyl, or a group of the formula: ##STR1## wherein each of R₆, R₇, and R₈ is selected from hydrogen, alkyl, or aryl;

(e) the total mole percentage of all --(RO)-- unit linking groups relative to all said units in Y is from zero to about 20 percent;

(f) R2 is hydrogen or Y;

(g) R is --CH₂ CH₂ --, --CH(CH₃)CH₂ --, --CH(C₂ H₅)CH₂ -- or mixtures thereof;

(h) the chromophore is an unsubstituted phthalocyanine of Cu, Ni, or Al;

(i) the polymeric or resinous material composition contains from about 0.001 to about 10.0 weight percent of one or a mixture of any of the colorants as defined above;

(j) the material is thermoplastic;

(k) the material is polyurethane;

(1) --D--Z-- is selected from --O--arylene--, --S--arylene--, --SO₂ --arylene--, --N(R₃)--arylene--, --N(SO₂ R₄)--arylene--, or --O--alkylene--O--arylene--;

(m) and the process for preparing the colorant comprises reacting at a temperature of e.g., from about 0° C. to about 100° C., metallophthalocyanine of the formula; A--(D--Z--SO₂ X)₁₋₁₆ with at least a stoichiometric quantity of an amine of the formula; HN(R₂)Y wherein X is selected from Cl, F, Br, I, or alkoxy, and A, R₂, D, Z, and Y are as defined above. Preferred reaction media include water, alcohols or ethers containing acid acceptors such as alkali metal carbonates, hydroxide or tertiary amines. Other more specific and preferred process embodiments will hereinafter become evident.

With reference to the above general formula for the colorant, the phthalocyanine chromophore can be provided with one to sixteen --D--Z--SO₂ X groups, each of which can be reacted with a reactive amine group HN(R₂)-- which can be on the same or different ones of the poly(oxyalkylene) moieties Y. In this retard it is noted that where the Y moiety is large, steric hinderance is less likely to interfere with the reaction of multiple HN(R₂)-- groups spaced thereon with multiple --SO₂ X groups on the same phthalocyanine chromophore.

The arylene moiety Z includes mono- and multi cyclic hydrocarbon nuclei, unsubstituted or substituted, such as that of benzene, naphthalene, anthracene, and biphenyl, of various heterocyclic nuclei, unsubstituted or substituted, such as that of thiophene, benzothiazole, benzoxazole, furan, thiazole, thiadiazole, or quinoline, and various combinations of such hydrocarbon and heterocyclic nuclei. Specific ones of such Z moieties are given in the tables below.

The linking group D preferably is selected from --Q--, --Q--alkylene--, --Q--alkylene--Q--, --Q--arylene--, --Q--arylene--Q--, --Q--cycloalkylene--Q--, --Q--alkylene-cycloalkylene-alkylene--Q--, or --Q--alkylene-arylene-alkylene--Q--, wherein Q is selected from --O--, --S--, --SO₂ --, --N(R₃)--, or --N(SO₂ R₄)--.

Thermoplastic resins which may be used according to the present invention include a wide range of synthetic resins and synthetic resin compositions which are known in the art as being essentially thermoplastic in nature. The term "thermoplastic" is used herein in its conventional sense to mean a resin "having the property of softening or fusing when heated and of hardening again when cooled" (see Webster's Seventh Collegiate Dictionary, G & C Merriam Co., 1985). Thermoplastic resins are to be clearly distinguished both in terms of their essential physical and chemical characteristics from thermosetting resins. The term "thermosetting" used herein is also used in its conventional sense to means a resin "having the property of becoming permanently rigid when heated or cured".

Examples of thermoplastic resin systems which may be employed include a wide range of polyolefin polymers, e.g., polyethylene, linear low density polyethylene, polypropylene, polybutylene and copolymers made from ethylene, propylene and/or butylene. Other thermoplastic polymers which may be employed according to the present invention include polyvinyl chloride, polyvinylidene chloride, cellulosic resins such as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate, acrylic resins such as polymethyl methacrylate, styrene acrylonitrile, polystyrene, polycarbonate and acrylonitrile butadiene styrene (therein ABS). polyamides such as nylon 6 and nylon 66 and polyesters such as polyethylene terephthalate, especially glycol modified polyethylene terephthalate and polybutylene terephthalate.

As mentioned above, the colorants may be employed in the thermoplastic resins in a minor amount sufficient to provide the desired degree of coloration in the resin. The actual amount used will, in addition to the desired depth of shade, depend upon the tinctorial strength of the chromophore used and the overall molecular weight of the colorant, e.g., chromophore plus poly(oxyalkylene) chain length. Typically the amount of colorant employed may be from about 0.0001 percent to about 10 percent, preferably from about 0.001 percent to about 3 percent, and most preferably from about 0.1 to about 1.0 percent by weight based upon the overall weight of the resin composition.

Other conventional additives may also be present in the resin compositions of the present invention. For instance, such additives may include plasticizers, antioxidants, stabilizers, lubricants, flame retardants, nucleating agents and other additives which will be readily identified by those skilled in the art. In general, the colorants have been observed to have little or no adverse interactions with these conventional additives.

Because the colorants if used properly ordinarily do not detract from the clarity of the resin, it has been found that additives which improve the clarity of such resins may be particularly desirable for use in combination with colorants as described herein to provide resin products that are both colored and which also have excellent clarity. One particular class of additives which have been found to be useful in this regard are the benzylidene sorbitols including substituted benzylidene sorbitols such as those described in U.S. Pat. No. 4,016,118 to Hamada, et al. (E.C. Chemical); U.S. Pat. No. 4,371,645 to Mahaffey (Milliken Research Corporation); and Japanese Pat. No. SHO [1977] 53-17044 to Kobsyashi, et al.(New Japan Chemical); all of these patents being hereby incorporated herein by reference.

The particular shade of the colorant will depend primarily upon the particular chromophore group selected. A large variety of colors and shades may be obtained by blending two or more colorants. Blending the colorants of the present invention can be readily accomplished as the colorants are polymeric materials which may have substantially identical solubility characteristics, which are dictated by the nature of the polymeric chain. Therefore, the colorants are in general soluble in one another, and are also in general completely compatible with each other.

According to the process of the invention, the colorant may be incorporated into the thermoplastic resin using conventional techniques such as those employed to incorporate other additives in such resins. For instance, the colorant may be incorporated into the resin by simply adding it to the resin while the resin is in a plasticized or molten state, typically prior to formation of the polymer into its final shape, e.g., by molding, extrusion, blow-molding and the like. For instance when the thermoplastic resin to be colored is a polyolefin resin the process may be carried out by adding a colorant comprised of a poly(oxyalkylene) substituted chromophore group directly to the molten polymer, by tumbling it onto a pre-extruded pelletized resin, or by mixing it into the resin powder prior to extrusion. The polymer may then be molded or extruded in the usual manner, i.e., in the same way as for polyolefin resins which are not colored. Details about these procedures may be found in the relevant literature.

Alternatively, a concentrate of the colorant in an appropriate resin or vehicle may first be prepared. Such concentrate may contain an appropriate-y high percentage of colorant. The concentrates may be in the form of liquids, solids, e.g., powders, pellets, etc., as may be desired. These concentrates may then be incorporated into the thermoplastic resin as is well understood in the art.

The colorants used in the process and in the composition of the present invention are polymeric colorants which may according to one embodiment be in the liquid phase. Thus, if in the liquid phase, they may be added to the thermoplastic polymer melt in solvent-free form rather than in the form of solutions or dispersions in a suitable solvent or dispersing medium. Obviously liquids may have certain processing advantages over solids, and moreover liquids may, if desired, be added directly to the molten polymer and therefore contain no extraneous solvent or dispersing agents. This process may, therefore, provide unusual and advantageous properties in the final thermoplastic resin product. Alternatively, however, the colorants may be premixed with minor amounts of a solvent or dispersing agent which is compatible with the resin, thus providing certain processing advantages.

According to the process of the invention, the liquid colorant may be incorporated into the thermosetting resins by simply adding it to the reaction mixture or to one of the components of the reaction mixture before or during the polyaddition reaction. For instance, when the thermosetting resin to be colored is a polyurethane resin the process may be carried out by adding the coloring agent in the form of a liquid to the polyol or even in some instances to the polyisocyanate component of the reaction mixture with before or during polyurethane formation. The subsequent reaction may be carried out in the usual manner, i.e., in the same way as for polyurethane resins which are not colored. Details about this procedure may be found in the relevant literature.

The present coloring agents of one embodiment of the present invention are polymeric, liquid, reactive coloring agents. Thus, they may be added to the reaction mixture or to one of the components thereof in solvent-free form rather than in the form of solutions or dispersions in suitable solvent or dispersing medium. Obviously liquids have significant processing advantages over solids, and moreover liquids of the present invention may, if desired, be added directly to the reaction mixture and therefore contain no extraneous nonreactive solvent or dispersing agent. This process may, therefore, provide unusual and advantageous properties in the final thermoset resin product. Alternatively, however, the coloring agent may be premixed with minor amounts of one or more of the precursors of the polymeric product, thus providing certain processing advantages.

The thermosetting resins to which the process of the present invention may be applied may be made by the reaction of a nucleophile with an electrophile. Examples of such resins include alkyds, allylics, the amines, e.g., melamine and urea, epoxies, phenolics, polyesters, silicones and urethanes. The thermosetting resin colored according to the present invention can be used in a variety of different end uses. e.g., as moldings, sealants, elastomers, films, fibers, lacquers, coating and foamed materials. It has been found in particular that the present colorants may quite advantageously be employed for the production of foams, such as polyurethane foams which may be soft, semi rigid or rigid foams, or the so-called polyurethane integral skin and microcellular foams. Such foams are useful for producing shaped products by injection molding, extrusion or calendaring and may be obtained by adding the liquid coloring agent to the polyol or diol component of the reaction mixture, or to one of the other components, although addition to the polyol component is preferred. The polyols may be polyesters which contain hydroxyl groups, in particular reaction products of dihydric alcohols and dibasic carboxylic acids, or polyethers which contain hydroxyl groups, in particular products of the addition of ethylene oxide, propylene oxide, styrene oxide or epichlorohydrin to water, alcohols or amines, preferably dialcohols. The colorant may also be admixed with chain extending diols, e.g., ethylene glycol, diethylene glycol and butane diol. In general, it is desirable not to use more than about 20 percent by weight of colorant based on the weight of polyol. In most cases very strong colorations are produced with a small proportion of the colorant, for example, from about 0.005 to about 2 percent, preferably 0.05 to 1 percent by weight colorant based on the weight of polyol.

Because the present colorants are, in themselves, polymeric compounds, they may be soluble, for instance, in most polyols which would be used in polyurethane manufacture, in most epoxy formulations, in polyester formulations and themselves in admixtures. This property may be particularly valuable in that this solubility may permit rapid mixing and homogeneous distribution throughout the resin, thus eliminating shading differences and streaks when properly mixed, the colorant may have no tendency to settle as would be the case with pigment dispersions, and it is possible to prepare a blend of two or more colorants which provides a wide range of color availability.

The present liquid reactive coloring agents may also be of considerable value in reaction injection molding (RIM) applications. The RIM process is a method of producing molded polyurethanes and other polymers wherein the two reactive streams are mixed while being poured into a mold. Upon reaction, the polymer is "blown" by chemicals to produce a foam structure. This process may be hindered by the presence of solid particles, such as conventional pigments. The present invention may not cause this hindrance because there are no particles in the system and the colorant becomes part of the polymer through reaction with one of the components.

General methods for preparing the colorants include the following two routes: ##STR2##

Route 1 involves the reaction of a phthalonitrile moiety containing a leaving group B(I), such as nitro or halogen, with a nucleophile(II). This reaction is preferably carried out in polar high-boiling solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidinone[A. W. Snow & J. R. Griffth, Marcomolecules, 17(1614-1624)]. Intermediates(III) are converted into metallophthalocyanines(IV) by known techniques using metals ions. Intermediates (IV) are then chlorosulfonated using excess chlorosulfonic acid at about 0°-30° C. to introduce chlorosulfonyl groups into the Z ring of (IV). If chlorosulfonation is desired also on the phthalocyanine ring itself, higher temperatures may be employed. Compounds (V) are then reacted with amines(VI) to give the desired phthalocyanine containing polyalkyleneoxy moiety Y.

Route 2 involves the reaction of a metallophthalocyanine containing 1-16 halogens(VII) with nucleophile(II) to give (VIII), a metallophthalocyanine moiety which contains 1 to 16 groups of the formula --D--Z [BASF, BP 1,537,375]. This nucleophilic displacement reaction is preferably carried out in at a high temperature in a polar high-boiling solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidinone. Chlorosulfonation at low temperature again gives compounds(V), which may contain a multiplicity of --D--Z--SO₂ Cl groups. Compounds(V) are then reacted with amines(VI) to give the sulfonamide derivatives of the invention.

Obviously, many variations of the above reactions are possible. For example, in Route 1, intermediate(III) may be mixed with unsubstituted or substituted phthalonitriles containing a wide variety of substituents such as halogen, lower alkyl, lower alkoxy, alkylthio, arylthio, etc. and the mixture treated with metal ions to give metallophthalocyanines containing a wide variety of substituents. These intermediates may be chlorosulfonated and the corresponding sulfonyl chlorides reacted with amines(VI) to give highly substituted metallophthalocyanines containing the polyalkyleneoxy moiety Y.

Commercially available and preferred amines(VI) from which the present preferred colorants are prepared are the JEFFAMINE series described in Texaco Chemical Company, New Product Development brochures as the M, D, ED, DU, BUD, T, MNPA: and EDR series: the disclosures of which are incorporated herein by reference and copies of which are transmitted herewith.

The preferred amines(VI) finding special utility in the present Invention are as follows:

R₉ --O(C₂ H₄ O)_(a) [CH₂ CH(CH₃)O]_(b) CH₂ CH(CH₃)NH₂

R₉ --O(C₂ H₄ O)_(a) [CH₂ CH(C₂ H₅)O]_(b) CH₂ CH(CH₃)NH₂

R₉ --O(C₂ H₄ O)_(a) [CH₂ CH(C₂ H₅)O]_(b) CH₂ CH(C₂ H₅)NH₂

R₉ --O(C₂ H₄ O)_(a) [CH₂ CH(CH₃)O]_(b) CH₂ CH(C₂ H₅)NH₂

R₉ --O[CH₂ CH(CH₃)O]_(a) CH₂ CH(CH₃)NH₂

R₉ --O[CH₂ CH(C₂ H₅)O]_(a) CH₂ CH(C₂ H₅)NH₂

R₉ --O[CH₂ CH(C₂ H₅)O]_(a) CH₂ CH(CH₃)NH₂

R₉ --O[CH₂ CH(CH₃)O]_(a) CH₂ CH(C₂ H₅)NH₂

wherein a=1-19; b=2-31; and R₉ is selected from CH₃, C₂ H₅, n--C₃ H₇, n--C₄ H₉, n--C₅ H₁₁, or n--C₆ H₁₃. ##STR3## wherein a=1-19; b=2-31; and R₁₀ is selected from CH₃, C₂ H₅, C₄ H₉, C₉ H₁₉, OCH₃, OC₂ H₅, or OC₄ H₉. ##STR4## wherein a=1-19; b=2-31; and R₁₁ is selected from hydrogen, CH₃, or C₂ H₅. ##STR5## wherein a=1-19; b=2-31. ##STR6## wherein a=1-19; b=2-31; and R₁₁ is recited above. H₂ NCH(CH₃)CH₂ [OCH(CH₃)CH₂ ]_(a) (OCH₂ CH₂)_(b) [OCH₂ CH(CH₃)]_(c) NH₂

H₂ NCH(CH₃)CH₂ [OCH(C₂ H₅)CH₂ ]_(a) (OCH₂ CH₂)_(b) [OCH₂ CH(CH₃)]_(c) NH₂

H₂ NCH(CH₃)CH₂ [OCH(C₂ H₅)CH₂ ]_(a) (OCH₂ CH₂)_(b) [OCH₂ CH(C₂ H₅)]_(c) NH₂

H₂ NCH(C₂ H₅)CH₂ [OCH(C₂ H₅)CH₂ ]_(a) (OCH₂ CH₂)_(b) [OCH₂ CH(C₂ H₅)]_(c) NH₂

H₂ NCH(C₂ H₅)CH₂ [OCH(CH₃)CH₂ ]_(a) (OCH₂ CH₂)_(b) [OCH₂ CH(C₂ H₅)]_(c) NH₂

H₂ NCH(CH₃)CH₂ [OCH(CH₃)CH₂ ]_(a) NH₂

H₂ NCH(C₂ H₅)CH₂ [OCH(C₂ H₅)CH₂ ]_(a) NH₂

wherein b=4-132; and a+c=2-5.

H₂ N(CH₃)CHCH₂ [OCH₂ CH(CH₃)]_(a) HN(CO)NH[CH(CH₃)CH₂ O]_(b) CH₂ CH(CH₃)NH₂

H₂ N(C₂ H₅)CHCH₂ [OCH₂ CH(C₂ H₅)]_(a) HN(CO)NH[CH(C₂ H₅)CH₂ O]_(b) CH₂ CH(C₂ H₅)NH₂

H₂ N(CH₃)CHCH₂ [OCH₂ CH(C₂ H₅)]_(a) HN(CO)NH[CH(C₂ H₅)CH₂ O]_(b) CH₂ CH(CH₃)NH₂

H₂ N(C₂ H₅)CHCH₂ [OCH₂ CH(CH₃)]_(a) HN(CO)NH[CH(CH₃)CH₂ O]_(b) CH₂ CH(C₂ H₅)NH₂

wherein a=2-68 and b=2-68.

HOCH(CH₃)CH₂ NHCH(CH₃)CH₂ [OCH₂ CH(CH₃)]_(a) NHCH₂ CH(CH₃)OH

wherein a is 2.6. ##STR7## wherein a+b+c=1.80; and x+y+z=5-85; and R₁₁ is recited above.

The following examples illustrate preparation of the present colorants, parts and percentages, unless otherwise stated being by weight. The abbreviation EO, PO, and BO refer to --CH₂ CH₂ --, --CH(CH₃)CH₂ --, and --CH(C₂ H₅)CH₂ --, respectively.

EXAMPLE #1 ##STR8##

A mixture was prepared by adding 80.7 grams (0.11 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 25.7 grams sodium carbonate in 500 ml of water. The mixture was cooled to 10°-15° C. and 0.0242 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

Sulfonation of Copper Tetraphenoxyphthalocyanine ##STR9##

Thirty one grams (0.03 mole) of copper tetraphenoxyphthalocyanine were dissolved at less than 0° C. in 263 grams of chlorosulfuric acid. The cooling bath was removed and the solution was allowed to warm to room temperature over two hours. The solution was further heated to 30° C. for about two hours after which the heat was removed and the solution was allowed to stir overnight at room temperature. The solution was then poured very gradually into a stirred mixture of water and ice. The dull blue supsenion was filtered and washed with ice water several times.

Preparation of Copper Tetraphenoxyphthalocyanine ##STR10##

A mixture was prepared by adding of 147 grams (0.67 mole) of 4-phenoxyphthalonitrile, 16.6 grams (0.16 mole) of cuprous chloride to 2670 ml of Cellosolve. The mixture was heated at reflux. One hundred and two grams (0.67 mole) of DBU(1,8-diazabicyclo[5.4.0]-undec-7-ene were added to the reaction mixture. This mixture was then heated at reflux for about six hours. During this time the reaction proceeded and the mixture turned blue and a solid precipitated. The precipitate was collected by filtration, washed with 3 percent hydrochloric acid solution, water, then ethanol. The copper tetraphenoxypththalocyanine was obtained with a maximum absorbance at 680 nm.

Phenoxyphthalonitrile ##STR11##

A mixture was prepared by adding 104 grams (1.1 moles) of phenol, 173 grams (1 mole) of 4-nitrophthalonitrile, and 207 grams of potassium carbonate in 1667 ml of dimethylformamide. The mixture was heated to 70° C. and mechanically stirred. Samples were taken of this reaction mixture periodically and analyzed by GLC. After five hours, the reaction was complete. The 4-phenoxyphthalonitrile was isolated by quenching the crude reaction mixture in ice water. The product was further purified by washing the crude precipitate with dilute sodium carbonate and then water. Finally the 4-phenoxyphthalonitrile was vacuum dried at 60° C.

EXAMPLE #2 ##STR12##

A mixture was prepared by adding 91.0 grams (0.19 mole) of a primary amine with an amine equivalent weight of 2.10 meq/g) to 44.5 grams sodium carbonate in 400 ml of THF and 200 ml of water. The mixture was cooled to 10°-15° C. and 0.042 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

EXAMPLE #3 ##STR13##

A mixture was prepared by adding 81.7 grams (0.14 mole) of a primary amine with an amine equivalent weight of 1.68 meq/g) to 33.0 grams sodium carbonate in 400 ml of THF and 200 ml of water. The mixture was cooled to 10°-15° C. and 0.031 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

EXAMPLE #4 ##STR14##

A mixture was prepared by adding 244.8 grams (0.41 mole) of Jeffamine M-600 primary amine with an amine equivalent weight of 1.66 meq/g) to 103.9 grams sodium carbonate in 1000 ml of water. The mixture was cooled to 10°-15° C. and 0.098 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

EXAMPLE #5 ##STR15##

A mixture was prepared by adding 91.8 grams (0.20 mole) of a primary amine with an amine equivalent weight of 2.06 meq/g) to 33.4 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.0315 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

EXAMPLE #6 ##STR16##

A mixture was prepared by adding 241.4 grams (0.275 mole) of a primary amine with an amine equivalent weight of 2.70 meq/g) to 64.7 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.061 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 617 nm.

EXAMPLE #7 ##STR17##

One hundred and fifty grams (0.061 mole) of the acetal prepared in example six were added along with 100 ml of water to a three necked 250 ml flask equipped with overhead stirrer, heating mantle, and Dean Stark trap. The mixture was heated to 80° C. and 4 grams of 70% sulfuric acid were added. This reaction mixture was maintained at 80° C. until no more acetone could be detected overhead in the trap. The mixture was then cooled and the product was extracted into methylene chloride. The methylene chloride solution was separated, washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried methylene chloride solution was filtered and stripped under reduced pressure at 90° C. to give a blue product containing a hydroxyl band in the IR spectrum.

EXAMPLE #8 ##STR18##

A mixture was prepared by adding 107.3 grams (0.16 mole) of a primary amine with an amine equivalent weight of 1.43 meq/g) to 36.2 grams sodium carbonate in 200 ml of THF. The mixture was cooled to 10°-15° C. and 0.0242 mole of an aqueous wet cake of freshly prepared tetraphenoxy nickel phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 618 nm.

Sulfonation of Nickel Tetraphenoxyphthalocyanine ##STR19##

Thirty one grams (0.0344 mole) of nickel tetraphenoxyphthalocyanine were dissolved at less than 0° C. in 264 grams of chlorosulfuric acid. The cooling bath was removed and the solution was allowed to warm to room temperature over two hours. The solution was further heated to 30° C for about two hours after which the heat was removed and the solution was allowed to stir overnight at room temperature. The solution was then poured very gradually into a stirred mixture of water and ice. The dull blue supsenion was filtered and washed with ice water several times.

Preparation of Nickel Tetraphenoxyphthalocyanine ##STR20##

A mixture was prepared by adding of 44 grams (0.20 mole) of 4-phenoxyphthalonitrile, 12.4 grams (0.05 mole) of nickel(II) acetate tetrahydrate to 925 ml of Cellosolve. The mixture was heated at reflux collecting water in a Dean Stark trap. The trap was emptied of azeotrope several times to insure that water was removed and make-up Cellosolve solvent was added to keep the volume constant in the reaction vessel. Thirty one grams (0.20 mole) of DBU(1,8-diazabicyclo[5.4.0]-undec-7-ene were added to the reaction mixture. This mixture was then heated at reflux for about six hours. During this time the reaction proceeded and the mixture turned blue and a solid precipitated. The precipitate was collected by filtration, washed with 3 percent hydrochloric acid solution, water, then ethanol. A yield of 22.3 grams of nickel tetraphenoxypththalocyanine was obtained with maximum absorbance at 672 nm.

EXAMPLE #9 ##STR21##

A mixture was prepared by adding 71.4 grams (0.10 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 23.5 grams sodium carbonate in 500 ml of water. The mixture was cooled to 10°-15° C. and 0.022 mole of an aqueous wet cake of freshly prepared tetraphenoxy nickel phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid with maximum absorbance at 618 nm.

EXAMPLE #10 ##STR22##

A mixture was prepared by adding 133.2 grams (0.18 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 42.4 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.040 mole of an aqueous wet cake of freshly prepared tetraphenoxy cobalt phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue colorant.

Sulfonation of Cobalt Tetraphenoxyphthalocyanine ##STR23##

Thirty one grams (0.03 mole) of cobalt tetraphenoxyphthalocyanine were dissolved at less than 0° C. in 260 grams of chlorosulfuric acid. The cooling bath was removed and the solution was allowed to warm to room temperature over two hours. The solution was further heated to 30° C. for about two hours after which the heat was removed and the solution was allowed to stir overnight at room temperature. The solution was then poured very gradually into a stirred mixture of water and ice. The dull blue supsenion was filtered and washed with ice water several times.

Preparation of Cobalt Tetraphenoxyphthalocyanine ##STR24##

A mixture was prepare 147 grams 0.667 mole) of 4-phenoxyphthalonitrile, 20.8 grams (0.162 mole) of cobalt(II) chloride to 2632 ml of butyl Cellosolve. The mixture was heated at reflux. One hundred grams (0.667 mole) of DBU(1,8-diazabicyclo[5.4.0]-undec-7-ene were added to the reaction mixture. This mixture was then heated at reflux for about six hours. During this time the reaction proceeded and the mixture turned blue and a solid precipitated. The precipitate was collected by filtration, washed with 3 percent hydrochloric acid solution, water, then ethanol.

EXAMPLE #11 ##STR25##

A mixture was prepared by adding 100.0 grams (0.135 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 31.8 grams sodium carbonate in 400 ml of water. The mixture was cooled to 10°-15° C. and 0.030 mole of an aqueous wet cake of freshly prepared tetra-p-methoxyphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue liquid.

Sulfonation of Copper Tetra-p-methoxyphenoxyphthalocyanine ##STR26##

Thirty five grams (0.03 mole) of copper tetra-p-methoxyphenoxyphthalocyanine were dissolved at less than 0° C. in 263 grams of chlorosulfuric acid. The cooling bath was removed and the solution was allowed to warm to room temperature over two hours. The solution was further heated to 30° C. for about two hours after which the heat was removed and the solution was allowed to stir overnight at room temperature. The solution was then poured very gradually into a stirred mixture of water and ice. The dull blue supsenion was filtered and washed with ice water several times.

Preparation of Copper Tetra-p-methoxyphenoxyphthalocyanine ##STR27##

A mixture was prepare by adding of 164.5 grams (0.67 mole) of p-methoxyphenoxyphthalonitrile, 16.3 grams (0.166 mole) of cuprous chloride to 4000 ml of butyl Cellosolve. The mixture was heated at reflux. One hundred and two grams (0.67 mole) of DBU(1,8-diazabicyclo[5.4.0]-undec-7-ene were added to the reaction mixture. This mixture was then heated at reflux for about six hours. During this time the reaction proceeded and the mixture turned blue and a solid precipitated. The precipitate was collected by filtration, washed with 3 percent hydrochloric acid solution, water, then ethanol. The copper tetra-p-methoxyphenoxypththalocyanine was obtained with maximum absorbance at 680 nm.

P-Methoxyphenoxyphthalonitrile ##STR28##

A mixture was prepared by adding 136.4 grams (1.1 moles) of p-methoxyphenol, 173 grams (1 mole) of 4-nitrophthalonitrile, and 207 grams of potassium carbonate in 1667 ml of dimethylformamide. The mixture was heated to 70° C. and mechanically stirred. Samples were taken of this reaction mixture periodically and analyzed by GLC. After five hours, the reaction was complete. The p-methoxyphenoxyphthalonitrile was isolated by quenching the crude reaction mixture in ice water. The product was further purified by washing the crude precipitate with dilute sodium carbonate and then water. Finally the p-methoxyphenoxyphthalonitrile was vacuum dried at 60° C.

EXAMPLE #12 ##STR29##

A mixture was prepared by adding 108.4 grams (0.18 mole) of Jeffamine M-600 primary amine with an amine equivalent weight of 1.66 meq/g) to 42.4 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.040 mole of an aqueous wet cake of freshly prepared tetra-p-methoxyphenoxy nickel phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue colorant.

EXAMPLE #13 ##STR30##

A mixture was prepared by adding 133.3 grams (0.18 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 42.4 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.040 mole of an aqueous wet cake of freshly prepared tetra-p-methoxyphenoxy cobalt phthalocyanine sulfonyl chloride derivative (containing an average of about four chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue colorant.

EXAMPLE #14 ##STR31##

A mixture was prepared by adding 226.7 grams (0.306 mole) of a primary amine with an amine equivalent weight of 1.35 meq/g) to 72.1 grams sodium carbonate in 400 ml of THF. The mixture was cooled to 10°-15° C. and 0.034 mole of an aqueous wet cake of freshly prepared tetraphenoxy copper phthalocyanine sulfonyl chloride derivative (containing an average of about eight chlorosulfonyl groups per molecule) was added to the mixture. After the addition was complete, the mixture was warmed to 50° C. for an additional two hours to insure complete reaction. Three hundred ml of methylene chloride was added followed by 300 ml of water. The methylene chloride solution was separated from the salt water solution, further washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped under reduced pressure at 90° C. to give a blue colorant.

Sulfonation of Copper Tetraphenoxyphthalocyanine ##STR32##

Thirty one grams (0.03 mole) of copper tetraphenoxyphthalocyanine are dissolved less than 0° C. in 400 grams of chlorosulfuric acid. The cooling bath was removed and the solution was allowed to warm to room temperature over two hours. The solution was further heated to 70° C. for about two hours then at 130° C. for eight hours. The heat was removed and the solution was allowed to stir overnight at room temperature. The solution was then poured very gradually into a stirred mixture of water and ice. The dull blue supsenion was filtered and washed with ice water several times.

EXAMPLE #15

This example illustrates the use of polymeric phthalocyanine colorants in polyolefin systems. The following formations were preblended using a paddle type mixer and the colorant of example one:

    ______________________________________                                         *INGREDIENT                                                                    ______________________________________                                                                  Formulation 1                                         ______________________________________                                         4MF Polypropylene resin (Exxon 9142G)                                                                   99.47%                                                Irganox 1010 (Ciba-Geigy)                                                                               800     ppm                                           Millad 3940              2500    ppm                                           Calcium stearate         1000    ppm                                           Polymeric colorant (example #1)                                                                         1000    ppm                                                                    Formulation 2                                         ______________________________________                                         4MF Polypropylene resin (Exxon 9142G)                                                                   99.62%                                                Irganox 1010 (Ciba-Geigy)                                                                               800     ppm                                           TiO.sub.2                1000    ppm                                           Calcium stearate         1000    ppm                                           Polymeric colorant (example #1)                                                                         1000    ppm                                           ______________________________________                                          *Calcium stearate functions as a stabilizer; Irganox 1010 is a registered      trademark of CibaGeigy Corporation for a hindered phenol stabilizer;           Millard 3940 is a clarifier for polyolefins; TiO.sub.2 is a white pigment      which serves as an opacifier; 4MF Polypropylene resin (Exxon 9142G) is a       random copolymer of propylene and ethylene.                              

After mixing, the formulations shown above melt compounded on a Brabender Twin Screw Mixer with a stock temperature of 245°-250° C. The compounded samples were then injection molded on a small toggle clamp machine into two-step plaques with thickness of 50 and 85 mils.

Formulation #1 had good clarity and was a deep cyan shade. Formulation #2 was opaque and had a medium cyan shade. Both formulations processed well in addition to having properties such as excellent heat stability, non-nucleation, non-migration and ease of resin clean up.

EXAMPLE #16

This example illustrates the use of polymeric phthalocyanine colorants in polyurethane. A polyurethane foam was prepared using the colorant of example seven in the formulation shown below:

    ______________________________________                                         Niax 16-56 Polyol (Union Carbide Corp.)                                                                  100    g                                             Water                     4.8    ml                                            Dabco 33 LV (Air Products)                                                                               0.31   ml                                            T-9 Catalyst (MIT Chemical Co.)                                                                          0.2    ml                                            L-520 Silicone (Union Carbide Corp.)                                                                     1.5    ml                                            Methylene Chloride        5.4    ml                                            Toluene Diisocyanate      55     ml                                            Colorant (example #7)     1      g                                             ______________________________________                                    

This foam was cured for one hour at 160° F. to give an even, bright, aqua blue shade. The polymeric colorant was not extractable with methanol, indicating that the colorant had copolymerized into the polyurethane structure.

                                      TABLE 1                                      __________________________________________________________________________      ##STR33##                                                                     Example                                                                             M  n (R.sub.1).sub.1-12                                                                     DZ           N(R.sub.2)   W  Y                               __________________________________________________________________________     1    Cu 2 tetra-Me                                                                               4-OC.sub.6 H.sub.4                                                                          NH           Me 2PO/7EO                         2    Cu 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             6BO/6EO                                                              3    Ni 3 H                                                                    4-OC.sub.6 H.sub.4                                                                  N(C.sub.2 H.sub.5 )                                                               Me                                                                               2PO/10EO                                                             4    Ni 4 tetra-Me                                                             4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/3EO                                                              5    Al 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  N(C.sub.6 H.sub.5)                                                                Me                                                                               4PO/3EO                                                              6    Al 4 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/4EO                                                              7    Cu 1 di-Cl                                                                3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               2PO/14EO                                                             8    Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                          N(C.sub.6 H.sub.11)                                                               Me                                                                               4PO/3EO                                                              9    Cu 3 tetra-Cl                                                             3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               9PO/1EO                                                              10   Cu 4 H                                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               2BO/6EO                                                              11   Cu 1 tetra-Br                                                             5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH Me                                                                               5PO/3EO                                                              12   Al 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          N(CH.sub.2 C.sub.6 H.sub.5)                                                       Me                                                                               2PO/10EO                                                             13   Cu 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH n-Bu                                                                             2BO/3EO                                                              14   Cu 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH Me                                                                               4PO/3EO                                                              15   Mn 3 tetra-I                                                              5-OC.sub.6 H.sub.3 (2-OMe)                                                          N(Me)                                                                             Me                                                                               9PO/1EO                                                              16   Cu 4 H                                                                    5-OC.sub. 6 H.sub.3 (2-OMe)                                                         NH n-Bu                                                                             3BO/6EO                                                              17   Cu 3 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          N(n-C.sub.4 H.sub.9)                                                              n-Bu                                                                             2BO/3EO                                                              18   Fe 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH n-Bu                                                                             4BO/3EO                                                              19   Cu 1 H                                                                    4-OC.sub.6 H.sub.3 (3-OMe)                                                          NH C.sub.6 H.sub.5                                                                  2BO/6EO                                                              20   Cu 2 tetra-OMe                                                            4-OC.sub.6 H.sub.3 (3-OMe)                                                          NH Me                                                                               4PO/3EO                                                              21   Cu 3 H                                                                    4-OC.sub.6 H.sub.3 (3-OMe)                                                          N(CH.sub.3)                                                                       Me                                                                               9PO/1EO                                                              22   Cr 4 H                                                                    4-OC.sub.6 H.sub.3 (3-OMe)                                                          N(CH.sub.3)                                                                       Me                                                                               2PO/7EO                                                              23   Cu 1 di-OMe                                                               5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                     N(CH.sub.3)                                                                       Me                                                                               3BO/4EO                                                              24   Cu 2 H                                                                    5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                     NH Me                                                                               10 EO                                                                25   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/14EO                                                             26   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               4PO/3EO                                                              27   Cu 3 di-Et                                                                3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/8EO                                                              28   Cr 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                            N(C.sub.2 H.sub.5)                                                               Me                                                                               2PO/7EO                                                              29   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/4EO                                                              30   Cu 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               12 EO                                                                31   Cu 1 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              32   Cu 2 tetra-t-C.sub.4 H.sub.9                                              5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               2BO/6EO                                                              33   Cu 3 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               2PO/1EO                                                              34   Cu 4 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           N(CH.sub.3)                                                                       Me                                                                               2PO/7EO                                                              35   Cu 2 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               2PO/4EO                                                              36   Cu 4 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               3BO/3EO                                                              37   Cu 1 H                                                                    4-OC.sub.6 H.sub.3 (3-Me)                                                           NH Me                                                                               2PO/6EO                                                              38   Cu 2 di-Br                                                                4-OC.sub.6 H.sub.3 (3-Me)                                                           NH Me                                                                               2PO/10EO                                                             39   Cu 3 H                                                                    4-OC.sub.6 H.sub.3 (3-Me)                                                           NH Me                                                                               3PO/4EO                                                              40   Cu 4 H                                                                    4-OC.sub.6 H.sub.3 (3-Me)                                                           NH Me                                                                               8PO/2EO                                                              41   Cu 1 H                                                                    5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                      N(C.sub.6 H.sub.11)                                                               Me                                                                               3PO/6EO                                                              42   Cu 2 H                                                                    5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                      NH Me                                                                               4PO/3EO                                                              43   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-OEt)                                                          NH Me                                                                               3BO/10EO                                                             44   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Et)                                                           NH n-Bu                                                                             2BO/4EO                                                              45   Cu 3 H                                                                    3-OC.sub.6 H.sub.3 (4-OEt)                                                          NH n-Bu                                                                             8PO/8EO                                                              46   Cu 4 H                                                                    3-OC.sub.6 H.sub.3 (4-OEt)                                                          NH Me                                                                               2PO/6EO                                                              47   Cu 2 di-OMe                                                               5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH Me                                                                               2PO/8EO                                                              48   Cu 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH Me                                                                               4PO/3EO                                                              49   Cu 3 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH n-Bu                                                                             2BO/4EO                                                              50   Cu 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH Me                                                                               2PO/7EO                                                              51   Cu 3 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH n-Bu                                                                             8PO/8EO                                                              52   Cu 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          NH Me                                                                               2PO/5EO                                                              53   Cu 2 di-I                                                                 4-OC.sub.6 H.sub.3 (3-OEt)                                                          NH C.sub.6 H.sub.5                                                                  2PO/4EO                                                              54   Cu 2 H                                                                    4-OC.sub.6 H.sub.3 (3-OEt)                                                          NH Me                                                                               4PO/3EO                                                              55   Cu 3 H                                                                    4-OC.sub.6 H.sub.3 (3-OEt)                                                          NH Me                                                                               9PO/1EO                                                              56   Cu 4 H                                                                    4-OC.sub.6 H.sub.3 (3-OEt)                                                          NH Me                                                                               5PO/3EO                                                              57   Cu 2 di-Cl                                                                3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/10EO                                                             58   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              59   Cu 3 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               6PO/6EO                                                              60   Cu 4 tetra-Cl                                                             3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/7EO                                                              61   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              62   Cu 4 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               3PO/5EO                                                              63   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               2PO/10EO                                                             64   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               4PO/3EO                                                              65   Cu 3 H                                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               6PO/6EO                                                              66   Cu 4 tetra-Et                                                             3-OC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               2PO/7EO                                                              67   Cu 2 H                                                                    5-OC.sub.6 H.sub.3 (2-Cl)                                                           NH Me                                                                               4BO/4EO                                                              68   Cu 2 H                                                                    5-OC.sub.6 H.sub.3 (2-Cl)                                                           NH Me                                                                               4PO/3EO                                                              69   Cu 3 H                                                                    5-OC.sub.6 H.sub.3 (2-Cl)                                                           NH Me                                                                               3PO/3EO                                                              70   Cu 4 tetra-Br                                                             5-OC.sub.6 H.sub.3 (2-Cl)                                                           NH Me                                                                               2PO/7EO                                                              71   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Br)                                                           NH Me                                                                               2PO/31EO                                                             72   Cu 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Br)                                                           NH Me                                                                               4PO/3EO                                                              73   Cu 3 H                                                                    3-OC.sub.6 H.sub.3 (4-Br)                                                           NH Et                                                                               9PO/1EO                                                              74   Cu 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Br)                                                           N(CH.sub.3)                                                                       Me                                                                               2PO/7EO                                                              75   Cu 2 H                                                                    4-SC.sub.6 H.sub.4                                                                  N(C.sub.2 H.sub.5)                                                                Me                                                                               6PO/3EO                                                              76   Cu 2 tri-Cl                                                               4-SC.sub.6 H.sub.4                                                                  N(CH.sub.2 C.sub.6 H.sub.5)                                                       n-Bu                                                                             6BO/6EO                                                              77   Cu 3 H                                                                    4-SC.sub.6 H.sub.4                                                                  N(iso-C.sub.3 H.sub.7)                                                            Me                                                                               2PO/10EO                                                             78   Cu 4 H                                                                    4-SC.sub.6 H.sub.4                                                                  N[(6EO)C.sub.6 H.sub.13 ]                                                         n-Bu                                                                             2BO/3EO                                                              79   Cu 2 H                                                                    4-SC.sub.6 H.sub.4                                                                   N[(2EO/3PO)Me]                                                                   Me                                                                               2PO/4EO                                                              80   Cu 4 H                                                                    4-SC.sub.6 H.sub.4                                                                  N[(4EO)C.sub.6 H.sub.13 ]                                                         Me                                                                               2PO/6EO                                                              81   Cu 2 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          N(CH.sub.2 C.sub.6 H.sub.13)                                                      n-Bu                                                                             8PO/8EO                                                              82   Cu 2 tetra-OEt                                                            3-SC.sub.6 H.sub.3 (4-OMe)                                                          N(iso-C.sub.4 H.sub.9)                                                            Me                                                                               4PO/3EO                                                              83   Cu 3 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          N(C.sub.6 H.sub.11)                                                               Me                                                                               9PO/1EO                                                              84   Cu 4 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          N(C.sub.6 H.sub.5)                                                                Me                                                                               2PO/7EO                                                              85   Cu 2 di-OEt                                                               3-SC.sub.6 H.sub.3 (4-Me)                                                           N(C.sub.2 H.sub.4 OH)                                                             Me                                                                               5PO/5EO                                                              86   Cu 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               4PO/3EO                                                              87   Cu 3 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               3BO/2EO                                                              88   Cu 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/5EO                                                              89   Cu 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              90   Cu 4 H                                                                    [3-SC.sub.6 H.sub.3 (4-Me)                                                          NH n-Bu                                                                             3BO/2EO                                                              91   Cu 2 tri-Cl                                                               3-SC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               2PO/16EO                                                             92   Cu 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               4PO/3EO                                                              93   Cu 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Cl)                                                           N(CH.sub.3)                                                                       Me                                                                               4PO/2EO                                                              94   Cu 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Cl)                                                           N(CH.sub.3)                                                                       Me                                                                               2PO/7EO                                                              95   Ni 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/7EO                                                              96   Ni 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             6BO/6EO                                                              97   Ni 3 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/10EO                                                             98   Ni 4 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/3EO                                                              99   Ni 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH Me                                                                               4PO/3EO                                                              100  Ni 4 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/4EO                                                              101  Ni 1 tri-Br                                                               3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               2PO/14EO                                                             102  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               4PO/3EO                                                              103  Ni 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          N(CH.sub.2 C.sub.6 H.sub.5)                                                       Me                                                                               5PO/3EO                                                              104  Ni 2 di-OEt                                                               5-OC.sub.6 H.sub.3 (2-OMe)                                                          N(C.sub.2 H.sub.5)                                                                Me                                                                               2PO/10EO                                                             105  Ni 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH n-Bu                                                                             2BO/3EO                                                              106  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/14EO                                                             107  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               4PO/3EO                                                              108  Ni 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/7EO                                                              109  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/4EO                                                              110  Ni 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               12 EO                                                                111  Ni 2 tetra-Me                                                             5-OC.sub.6 H.sub.3 (2-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              112  Ni 2 di-OMe                                                               5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               2BO/6EO                                                              113  Ni 4 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               2PO/4EO                                                              114  Ni 4 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH Me                                                                               3BO/3EO                                                              115  Ni 4 H                                                                    5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                      NH Me                                                                               3PO/6EO                                                              116  Ni 2 H                                                                    5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                      NH Me                                                                               4PO/3EO                                                              117  Ni 2 di-I                                                                 3-OC.sub.6 H.sub.3 (4-OEt)                                                          NH Me                                                                               3BO/10EO                                                             118  Ni 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          N(CH.sub.3)                                                                       Me                                                                               2PO/8EO                                                              119  Ni 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                          N(CH.sub.3)                                                                       Me                                                                               4PO/3EO                                                              120  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/10EO                                                             121  Ni 4 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              122  Ni 2 di-Cl                                                                3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/7EO                                                              123  Ni 4 tetra-OEt                                                            3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              124  Ni 4 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               3PO/5EO                                                              125  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                           NH Me                                                                               2PO/10EO                                                             126  Ni 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                           N(iso-C.sub.3 H.sub.7 OH)                                                         Me                                                                               4PO/3EO                                                              127  Ni 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Br)                                                           N(C.sub.2 H.sub.4 OH)                                                             Me                                                                               2PO/7EO                                                              128  Ni 2 di-Br                                                                4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               6PO/3EO                                                              129  Ni 2 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             6BO/6EO                                                              130  Ni 3 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/10EO                                                             131  Ni 4 H                                                                    4-SC.sub.6 H.sub.4                                                                  N(2EO)                                                                            n-Bu                                                                             2BO/3EO                                                              132  Ni 2 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/4EO                                                              133  Ni 4 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/6EO                                                              134  Ni 2 di-Me                                                                3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               5PO/5EO                                                              135  Ni 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           N(CH.sub.3)                                                                       Me                                                                               4PO/3EO                                                              136  Ni 3 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           N(CH.sub.3)                                                                       Me                                                                               3BO/2EO                                                              137  Ni 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/5EO                                                              138  Ni 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              139  Ni 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH n-Bu                                                                             3BO/2EO                                                              140  Co 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  N(2PO)                                                                            Me                                                                               2PO/7EO                                                              142  Co 2 H                                                                    4-OC.sub.6 H.sub.4                                                                  N(2PO/1EO)                                                                        n-Bu                                                                             6BO/6EO                                                              143  Co 3 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/10EO                                                             144  Co 4 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/3EO                                                              145  Co 2 di-OEt                                                               4-OC.sub.6 H.sub.4                                                                  NH Me                                                                               4PO/3EO                                                              146  Co 4 H                                                                    4-OC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/4EO                                                              147  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                          N(CH.sub.2 C.sub.6 H.sub.5)                                                       Me                                                                               2PO/14EO                                                             148  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               4PO/3EO                                                              149  Co 2 tetra-O-t-C.sub.4 H.sub.9                                            3-OC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               2BO/6EO                                                              150  Co 2 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH Me                                                                               5PO/3EO                                                              151  Co 4 H                                                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                          NH Me                                                                               2PO/10EO                                                             152  Co 4 H                                                                    4-OC.sub.6 H.sub.3 (2-OMe)                                                          NH n-Bu                                                                             2BO/3EO                                                              153  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/14EO                                                             154  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           N(C.sub.2 H.sub.5)                                                                Me                                                                               4PO/3EO                                                              155  Co 2 tetra-O-n-C.sub.4 H.sub.9                                            3-OC.sub.6 H.sub.3 (4-Me)                                                           N(CH.sub.3)                                                                       Me                                                                               2PO/8EO                                                              156  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/7EO                                                              157  Co 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               2PO/4EO                                                              158  Co 4 H                                                                    3-OC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               12 EO                                                                159  Co 2 H                                                                    5-OC.sub.6 H.sub.3 (2-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              160  Co 2 di-Cl                                                                3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/10EO                                                             161  Co 2 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              162  Co 2 di-Me                                                                3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               2PO/7EO                                                              163  Co 4 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               4PO/3EO                                                              164  Co 4 H                                                                    3-OC.sub.6 H.sub.3 (4-t-Bu)                                                         NH Me                                                                               3PO/5EO                                                              165  Co 2 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               6PO/3EO                                                              166  Co 2 di-OEt                                                               4-SC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             6BO/6EO                                                              167  Co 3 H                                                                    4-SC.sub.6 H.sub.4                                                                  NH Me                                                                               2PO/10EO                                                             168  Co 4 tetra-OCOMe                                                          4-SC.sub.6 H.sub.4                                                                  NH n-Bu                                                                             2BO/3EO                                                              169  Co 3 H                                                                    4-SC.sub.6 H.sub.4                                                                  N(CH.sub.3)                                                                       Me                                                                               2PO/4EO                                                              170  Co 2 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          N(CH.sub.3)                                                                       n-Bu                                                                             8PO/8EO                                                              171  Co 2 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               4PO/3EO                                                              172  Co 4 H                                                                    3-SC.sub.6 H.sub.3 (4-OMe)                                                          NH Me                                                                               2PO/7EO                                                              173  Co 2 di-OCOMe                                                             3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               5PO/5EO                                                              174  Co 2 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH Me                                                                               4PO/3EO                                                              175  Co 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           N(C.sub.2 H.sub.4 OH)                                                             Me                                                                               2PO/5EO                                                              176  Co 2 tetra-Cl                                                             3-SC.sub.6 H.sub.3 (4-Me)                                                           NH n-Bu                                                                             2BO/4EO                                                              177  Co 4 H                                                                    3-SC.sub.6 H.sub.3 (4-Me)                                                           NH n-Bu                                                                             3BO/2EO                                                              __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     Example                                                                              A{DZSO.sub.2N(R.sub.2)YW}                            n                   __________________________________________________________________________            ##STR34##                                           2                   2                                                                                     ##STR35##                                           2                   3                                                                                     ##STR36##                                           4                   4                                                                                     ##STR37##                                           4                   5                                                                                     ##STR38##                                           2                   6                                                                                     ##STR39##                                           4                   7                                                                                     ##STR40##                                           3                   8                                                                                     ##STR41##                                           2                   9                                                                                     ##STR42##                                           4                   10                                                                                    ##STR43##                                           2                   11                                                                                    ##STR44##                                           4                   12                                                                                    ##STR45##                                           4                   13                                                                                    ##STR46##                                           2                   14                                                                                    ##STR47##                                           2                   15                                                                                    ##STR48##                                           4                   __________________________________________________________________________      ##STR49##                                                                

                                      TABLE 3                                      __________________________________________________________________________      ##STR50##                                                                     Example                                                                              M  n  (R.sub.1).sub.1-12                                                                     DZ           N(R.sub.2)                                                                            R.sub.5                                                                            Y                                  __________________________________________________________________________     1     Cu 2  H                                                                  4-OC.sub.6 H.sub.4               NH     H   3PO/1EO                            2     Cu 3  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH H  6BO/6EO                                                            3     Cu 2  tetra-Cl                                                           4-OC.sub.6 H.sub.4                                                                   NH H   2PO/10EO                                                          4     Cu 4  di-Cl                                                              4-OC.sub.6 H.sub.4                                                                   NH Me 2BO/3EO                                                            5     Cu 2  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH H  4PO/3EO                                                            6     Cu 4  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH H  2BO/4EO                                                            7     Cu 1  tri-Cl                                                             3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H   2PO/14EO                                                          8     Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            9     Cu 3  tetra-Br                                                           3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  9PO/1EO                                                            10    Cu 4  Me                                                                 3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  2BO/6EO                                                            11    Cu 2  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  5PO/3EO                                                            12    Cu 3  di-Me                                                              5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H   2PO/10EO                                                          13    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  2BO/3EO                                                            14    Cu 2  tri-Br                                                             5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  4PO/3EO                                                            15    Cu 3  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  9PO/1EO                                                            16    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH Me 3BO/6EO                                                            17    Cu 3  di-Cl                                                              5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH Me 2BO/3EO                                                            18    Cu 4  tetra-Et                                                           5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH Me 4BO/3EO                                                            19    Cu 2  H                                                                  4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH H  4PO/3EO                                                            20    Cu 2  H                                                                  4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH H  4PO/3EO                                                            21    Cu 3  tetra-Cl                                                           4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH H  9PO/1EO                                                            22    Cu 4  H                                                                  4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH H  2PO/7EO                                                            23    Cu 1  di-Br                                                              5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                      NH Me 3BO/4EO                                                            24    Cu 2  H                                                                  5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                      NH Me 10 EO                                                              25    Cu 1  di-OMe                                                             3-OC.sub.6 H.sub.3 (4-Me)                                                            NH Me  2PO/14EO                                                          26    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH Et 4PO/3EO                                                            27    Cu 3  H                                                                  3-OC.sub.6 H.sub. 3 (4-Me)                                                           NH H  2PO/8EO                                                            28    Cu 4  tetra-I                                                            3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/7EO                                                            29    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/4EO                                                            30    Cu 4  tetra-t-C.sub.4 H.sub.9                                            3-OC.sub.6 H.sub.3 (4-Me)                                                            NH Me 12 EO                                                              31    Cu 1  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH Me 2BO/4EO                                                            32    Cu 2  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH Et 2BO/6EO                                                            33    Cu 3  tetra-n-C.sub.4 H.sub.9                                            5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2PO/1EO                                                            34    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2PO/7EO                                                            35    Cu 2  tetra-Et                                                           5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2PO/4EO                                                            36    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  3BO/3EO                                                            37    Cu 1  di-Br                                                              4-OC.sub.6 H.sub.3 (3-Me)                                                            NH H  2PO/6EO                                                            38    Cu 2  H                                                                  4-OC.sub.6 H.sub.3 (3-Me)                                                            NH H   2PO/10EO                                                          39    Cu 3  di-I                                                               4-OC.sub.6 H.sub.3 (3-Me)                                                            NH H  3PO/4EO                                                            40    Cu 4  tetra-I                                                            4-OC.sub.6 H.sub.3 (3-Me)                                                            NH H  8PO/2EO                                                            41    Cu 1  H                                                                  5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH Me 3PO/6EO                                                            42    Cu 2  H                                                                  5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH Me 4PO/3EO                                                            43    Cu 1  tetra-Cl                                                           3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH Et  3BO/10EO                                                          44    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Et)                                                            NH Et 2BO/4EO                                                            45    Cu 3  H                                                                  3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH Et 8PO/8EO                                                            46    Cu 4  di-Br                                                              3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH Me 2PO/6EO                                                            47    Cu 1  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH Me 2PO/8EO                                                            48    Cu 1  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH Me 4PO/3EO                                                            49    Cu 3  tetra-Et                                                           5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH Me 2BO/4EO                                                            50    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH Me 2PO/7EO                                                            51    Cu 3  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH H  8PO/8EO                                                            52    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH H  2PO/5EO                                                            53    Cu 1  di-OCOMe                                                           4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH H  2PO/4EO                                                            54    Cu 2  H                                                                  4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH H  4PO/3EO                                                            55    Cu 3  H                                                                  4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH H  9PO/1EO                                                            56    Cu 4  H                                                                  4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH H  5PO/3EO                                                            57    Cu 1  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me  2PO/10EO                                                          58    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 4PO/3EO                                                            59    Cu 3  tetra-Br                                                           3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 6PO/6EO                                                            60    Cu 4  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Et 2PO/7EO                                                            61    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Et 4PO/3EO                                                            62    Cu 4  di-Cl                                                              3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Et 3PO/5EO                                                            63    Cu 1  tetra-Me                                                           3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH H   2PO/10EO                                                          64    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH H  4PO/3EO                                                            65    Cu 3  H                                                                  3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH H  6PO/6EO                                                            66    Cu 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Cl)                                                             NH                                                                               H  2PO/7EO                                                            67    Cu 1  di-Me                                                              5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH H  4BO/4EO                                                            68    Cu 2  H                                                                  5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH H  4PO/3EO                                                            69    Cu 3  H                                                                  5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH H  3PO/3EO                                                            70    Cu 4  H                                                                  5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH H  2PO/7EO                                                            71    Cu 1  H                                                                  3-OC.sub.6 H.sub.3 (4-Br)                                                            NH H   2PO/31EO                                                          72    Cu 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Br)                                                            NH H  4PO/3EO                                                            73    Cu 3  H                                                                  3-OC.sub.6 H.sub.3 (4-Br)                                                            NH H  9PO/1EO                                                            74    Cu 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Br)                                                            NH H  2PO/7EO                                                            75    Cu 1  tetra-Cl                                                           4-SC.sub.6 H.sub.4                                                                   NH H  6PO/3EO                                                            76    Cu 2  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH H  6BO/6EO                                                            77    Cu 3  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH Me  2PO/10EO                                                          78    Cu 4  tetra-Br                                                           4-SC.sub.6 H.sub.4                                                                   NH Me 2BO/3EO                                                            79    Cu 2  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH Me 2PO/4EO                                                            80    Cu 4  tetra-t-Bu                                                         4-SC.sub. 6 H.sub.4                                                                  NH Me 2PO/6EO                                                            81    Cu 1  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  8PO/8EO                                                            82    Cu 2  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            83    Cu 3  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            83    Cu 3  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  9PO/1EO                                                            84    Cu 4  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  2PO/7EO                                                            85    Cu 1  di-Cl                                                              3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  5PO/5EO                                                            86    Cu 2  tetra-Cl                                                           3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  4PO/3EO                                                            87    Cu 3  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  3BO/2EO                                                            88    Cu 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/5EO                                                            89    Cu 2  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH Me 2BO/4EO                                                            90    Cu 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH Me 3BO/2EO                                                            91    Cu 1  tri-Br                                                             3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH H   2PO/16EO                                                          92    Cu 2  H                                                                  3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH H  4PO/3EO                                                            93    Cu 3  H                                                                  3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH H  4PO/2EO                                                            94    Cu 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH H  2PO/7EO                                                            96    Ni 2  di-OMe                                                             4-OC.sub.6 H.sub.4                                                                   NH Me 6BO/6EO                                                            97    Ni 3  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me  2PO/10EO                                                          98    Ni 4  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me 2BO/3EO                                                            99    Ni 2  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me 4PO/3EO                                                            100   Ni 4  di-Cl                                                              4-OC.sub.6 H.sub.4                                                                   NH Me 2BO/4EO                                                            101   Ni 1  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H   2PO/14EO                                                          102   Ni 2  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            103   Ni 1  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  5PO/3EO                                                            104   Ni 2  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H   2PO/10EO                                                          105   Ni 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  2BO/3EO                                                            106   Ni 1  tetra-Me                                                           3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H   2PO/14EO                                                          107   Ni 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  4PO/3EO                                                            108   Ni 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/7EO                                                            109   Ni 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH Me 2PO/4EO                                                            110   Ni 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH Me 12 EO                                                              111   Ni 1  tetra-I                                                            5-OC.sub.6 H.sub.3 (2-Me)                                                            NH Et 2BO/4EO                                                            112   Ni 2  di-OEt                                                             5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2BO/6EO                                                            113   Ni 2  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2PO/4EO                                                            114   Ni 4  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  3BO/3EO                                                            115   Ni 1  H                                                                  5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH H  3PO/6EO                                                            116   Ni 2  tetra-Et                                                           5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH H  4PO/3EO                                                            117   Ni 1  H                                                                  3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH H   3BO/10EO                                                          118   Ni 1  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH H  2PO/8EO                                                            119   Ni 2  H                                                                  5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH H  4PO/3EO                                                            120   Ni 1  tetra-OMe                                                          3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me  2PO/10EO                                                          121   Ni 2  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 4PO/3EO                                                            122   Ni 4  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 2PO/7EO                                                            123   Ni 2  di-OMe                                                             3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 4PO/3EO                                                            124   Ni 4  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH Me 3PO/5EO                                                            125   Ni 1  H                                                                  3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH H   2PO/10EO                                                          126   Ni 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH H  4PO/3EO                                                            127   Ni 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Br)                                                            NH H  2PO/7EO                                                            128   Ni 1  tetra-I                                                            4-SC.sub.6 H.sub.4                                                                   NH H  6PO/3EO                                                            129   Ni 2  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH H  6BO/6EO                                                            130   Ni 3  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH Me  2PO/10EO                                                          131   Ni 4  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH Me 2BO/3EO                                                            132   Ni 2  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH Me 2PO/4EO                                                            133   Ni 4  di-OMe                                                             4-SC.sub.6 H.sub.4                                                                   NH H  2PO/6EO                                                            134   Ni 1  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  5PO/5EO                                                            135   Ni 2  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  4PO/3EO                                                            136   Ni 3  di-Br                                                              3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  3BO/2EO                                                            137   Ni 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/5EO                                                            138   Ni 2  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH Me 2BO/4EO                                                            139   Ni 4  tetra-Cl                                                           3-SC.sub.6 H.sub.3 (4-Me)                                                            NH Me 3BO/2EO                                                            140   Co 1  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me 2PO/7EO                                                            142   Co 2  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me 6BO/6EO                                                            143   Co 3  tetra-O-t-Bu                                                       4-OC.sub.6 H.sub.4                                                                   NH Me  2PO/10EO                                                          144   Co 4  H                                                                  4-OC.sub.6 H.sub.4                                                                   NH Me 2BO/3EO                                                            145   Co 2  di-I                                                               4-OC.sub.6 H.sub.4                                                                   NH Me 4PO/3EO                                                            146   Co 4  tetra-I                                                            4-OC.sub.6 H.sub.4                                                                   NH Me 2BO/4EO                                                            147   Co 1  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H   2PO/14EO                                                          148   Co 2  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            149   Co 4  H                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH H  2BO/6EO                                                            150   Co 1  H                                                                  3-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  5PO/3EO                                                            151   Co 2  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H   2PO/10EO                                                          152   Co 4  H                                                                  5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH H  2BO/3EO                                                            153   Co 1  di-Br                                                              3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H   2PO/14EO                                                          154   Co 2  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  4PO/3EO                                                            155   Co 3  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/8EO                                                            156   Co 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/7EO                                                            157   Co 2  di-Me                                                              3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/4EO                                                            158   Co 4  H                                                                  3-OC.sub.6 H.sub.3 (4-Me)                                                            NH H  12 EO                                                              159   Co 1  H                                                                  5-OC.sub.6 H.sub.3 (2-Me)                                                            NH H  2BO/4EO                                                            160   Co 1  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH H   2PO/10EO                                                          161   Co 2  H                                                                  3-OC.sub.6 H.sub. 3 (4-t-Bu)                                                         NH H  4PO/3EO                                                            162   Co 4  tetra-Cl                                                           3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH H  2PO/7EO                                                            163   Co 2  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH H  4PO/3EO                                                            164   Co 4  H                                                                  3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH H  3PO/5EO                                                            165   Co 1  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH H  6PO/3EO                                                            166   Co 2  di-OEt                                                             4-SC.sub.6 H.sub.4                                                                   NH H  6BO/6EO                                                            167   Co 3  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH H   2PO/10EO                                                          168   Co 4  H                                                                  4-SC.sub.6 H.sub.4                                                                   NH H  2BO/3EO                                                            169   Co 3  di-I                                                               4-SC.sub.6 H.sub.4                                                                   NH H  2PO/4EO                                                            170   Co 1  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  8PO/8EO                                                            171   Co 2  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  4PO/3EO                                                            172   Co 4  H                                                                  3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH H  2PO/7EO                                                            173   Co 1  tetra-Cl                                                           3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  5PO/5EO                                                            174   Co 2  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  4PO/3EO                                                            175   Co 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  2PO/5EO                                                            176   Co 2  tri-Cl                                                             3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  2BO/4EO                                                            177   Co 4  H                                                                  3-SC.sub.6 H.sub.3 (4-Me)                                                            NH H  3BO/2EO                                                            __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR51##                                                                     Example                                                                              M n  (R.sub.1).sub.1-12                                                                      DZ            N(R.sub.2)                                                                           R.sub.5                                                                           Y                                   __________________________________________________________________________     1     Cu                                                                               2  H                                                                   4-OC.sub.6 H.sub. 4               NH    H  3PO/1EO                             2     Cu                                                                               3  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               H  6BO/6EO                                                             3     Cu                                                                               2  tetra-Cl                                                            4-OC.sub.6 H.sub.4                                                                   NH                                                                               H   2PO/10EO                                                           4     Cu                                                                               4  di-OMe                                                              4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/3EO                                                             5     Cu                                                                               2  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               H  4PO/3EO                                                             6     Cu                                                                               4  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               H  2BO/4EO                                                             7     Cu                                                                               1  di-Br                                                               3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H   2PO/14EO                                                           8     Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  4PO/3EO                                                             9     Cu                                                                               3  tetra-I                                                             3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  9PO/1EO                                                             10    Cu                                                                               4  Me                                                                  3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  2BO/6EO                                                             11    Cu                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  5PO/3EO                                                             12    Cu                                                                               3  di-Et                                                               5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H   2PO/10EO                                                           13    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  2BO/3EO                                                             14    Cu                                                                               2  tri-Cl                                                              5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  4PO/3EO                                                             15    Cu                                                                               3  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  9PO/1EO                                                             16    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               Me 3BO/6EO                                                             17    Cu                                                                               3  di-I                                                                5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               Me 2BO/3EO                                                             18    Cu                                                                               4  tetra-Me                                                            5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               Me 4BO/3EO                                                             20    Cu                                                                               2  H                                                                   4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH                                                                               H  4PO/3EO                                                             21    Cu                                                                               3  tetra-Br                                                            4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH                                                                               H  9PO/1EO                                                             22    Cu                                                                               4  H                                                                   4-OC.sub.6 H.sub.3 (3-OMe)                                                           NH                                                                               H  2PO/7EO                                                             23    Cu                                                                               1  tri-Br                                                              5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                      NH                                                                               Me 3BO/4EO                                                             24    Cu                                                                               2  H                                                                   5-OC.sub.6 H.sub.2 (2,6-di-OMe)                                                      NH                                                                               Me 10 EO                                                               25    Cu                                                                               1  di-Cl                                                               3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me  2PO/14EO                                                           26    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Et 4PO/3EO                                                             27    Cu                                                                               3  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/8EO                                                             28    Cu                                                                               4  tetra-I                                                             3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/7EO                                                             29    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/4EO                                                             30    Cu                                                                               4  tetra-n-C.sub.4 H.sub.9                                             3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 12 EO                                                               31    Cu                                                                               1  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               Me 2BO/4EO                                                             32    Cu                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               Et 2BO/6EO                                                             33    Cu                                                                               2  tetra-t-C.sub.4 H.sub.9                                             5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2PO/1EO                                                             34    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2PO/7EO                                                             35    Cu                                                                               2  tetra-Me                                                            5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2PO/4EO                                                             36    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  3BO/3EO                                                             37    Cu                                                                               1  di-I                                                                4-OC.sub.6 H.sub.3 (3-Me)                                                            NH                                                                               H  2PO/6EO                                                             38    Cu                                                                               2  H                                                                   4-OC.sub.6 H.sub.3 (3-Me)                                                            NH                                                                               H   2PO/10EO                                                           39    Cu                                                                               3  di-Cl                                                               4-OC.sub.6 H.sub.3 (3-Me)                                                            NH                                                                               H  3PO/4EO                                                             40    Cu                                                                               4  tetra-I                                                             4-OC.sub.6 H.sub.3 (3-Me)                                                            NH                                                                               H  8PO/2EO                                                             41    Cu                                                                               1  H                                                                   5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH                                                                               Me 3PO/6EO                                                             42    Cu                                                                               2  H                                                                   5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH                                                                               Me 4PO/3EO                                                             43    Cu                                                                               1  tetra-Br                                                            3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH                                                                               Et  3BO/10EO                                                           44    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Et)                                                            NH                                                                               Et 2BO/4EO                                                             45    Cu                                                                               3  H                                                                   3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH                                                                               Et 8PO/8EO                                                             46    Cu                                                                               4  di-Cl                                                               3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH                                                                               Me 2PO/6EO                                                             47    Cu                                                                               1  tri-Cl                                                              5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               Me 2PO/8EO                                                             48    Cu                                                                               1  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               Me 4PO/3EO                                                             49    Cu                                                                               3  tetra-Et                                                            5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               Me 2BO/4EO                                                             50    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               Me 2PO/7EO                                                             51    Cu                                                                               3  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               H  8PO/8EO                                                             52    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               H  2PO/5EO                                                             53    Cu                                                                               1  di-OCOMe                                                            4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH                                                                               H  2PO/4EO                                                             54    Cu                                                                               2  H                                                                   4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH                                                                               H  4PO/3EO                                                             55    Cu                                                                               3  H                                                                   4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH                                                                               H  9PO/1EO                                                             56    Cu                                                                               4  H                                                                   4-OC.sub.6 H.sub.3 (3-OEt)                                                           NH                                                                               H  5PO/3EO                                                             57    Cu                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me  2PO/10EO                                                           58    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 4PO/3EO                                                             59    Cu                                                                               3  tetra-Br                                                            3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 6PO/6EO                                                             60    Cu                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Et 2PO/7EO                                                             61    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Et 4PO/3EO                                                             62    Cu                                                                               4  di-Br                                                               3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Et 3PO/5EO                                                             63    Cu                                                                               1  tetra-Et                                                            3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H   2PO/10EO                                                           64    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  4PO/3EO                                                             65    Cu                                                                               3  H                                                                   3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  6PO/6EO                                                             66    Cu                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  2PO/7EO                                                             67    Cu                                                                               1  di-OEt                                                              5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH                                                                               H  4BO/4EO                                                             68    Cu                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH                                                                               H  4PO/3EO                                                             69    Cu                                                                               3  H                                                                   5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH                                                                               H  3PO/3EO                                                             70    Cu                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-Cl)                                                            NH                                                                               H  2PO/7EO                                                             71    Cu                                                                               1  tri-Cl                                                              3-OC.sub.6 H.sub.3 (4-Br)                                                            NH                                                                               H   2PO/31EO                                                           72    Cu                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Br)                                                            NH                                                                               H  4PO/3EO                                                             73    Cu                                                                               3  H                                                                   3-OC.sub.6 H.sub.3 (4-Br)                                                            NH                                                                               H  9PO/1EO                                                             74    Cu                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Br)                                                            NH                                                                               H  2PO/7EO                                                             75    Cu                                                                               1  tetra-Br                                                            4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6PO/3EO                                                             76    Cu                                                                               2  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6BO/6EO                                                             77    Cu                                                                               3  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me  2PO/10EO                                                           78    Cu                                                                               4  tetra-Br                                                            4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/3EO                                                             79    Cu                                                                               2  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me 2PO/4EO                                                             80    Cu                                                                               4  tetra-n-C.sub.4 H.sub.9                                             4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me 2PO/6EO                                                             81    Cu                                                                               1  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  8PO/8EO                                                             82    Cu                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  4PO/3EO                                                             83    Cu                                                                               3  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  9PO/1EO                                                             84    Cu                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  2PO/7EO                                                             85    Cu                                                                               1  di-I                                                                3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  5PO/5EO                                                             86    Cu                                                                               2  tetra-I                                                             3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  4PO/3EO                                                             87    Cu                                                                               3  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  3BO/2EO                                                             88    Cu                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/5EO                                                             89    Cu                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 2BO/4EO                                                             90    Cu                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 3BO/2EO                                                             91    Cu                                                                               1  tri-I                                                               3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H   2PO/16EO                                                           92    Cu                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  4PO/3EO                                                             93    Cu                                                                               3  H                                                                   3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  4PO/2EO                                                             94    Cu                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  2PO/7EO                                                             96    Ni                                                                               2  di-OEt                                                              4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 6BO/6EO                                                             97    Ni                                                                               3  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me  2PO/10EO                                                           98    Ni                                                                               4  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/3EO                                                             99    Ni                                                                               2  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 4PO/3EO                                                             100   Ni                                                                               4  di-Br                                                               4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/4EO                                                             101   Ni                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H   2PO/14EO                                                           102   Ni                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  4PO/3EO                                                             103   Ni                                                                               1  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  5PO/3EO                                                             104   Ni                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H   2PO/10EO                                                           105   Ni                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  2BO/3EO                                                             106   Ni                                                                               1  tetra-OMe                                                           3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H   2PO/14EO                                                           107   Ni                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  4PO/3EO                                                             108   Ni                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/7EO                                                             109   Ni                                                                               2  H                                                                   3-OC.sub.6 H.sub. 3 (4-Me)                                                           NH                                                                               Me 2PO/4EO                                                             110   Ni                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 12 EO                                                               111   Ni                                                                               1  tetra-I                                                             5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               Et 2BO/4EO                                                             112   Ni                                                                               2  di-OMe                                                              5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2BO/6EO                                                             113   Ni                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2PO/4EO                                                             114   Ni                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  3BO/3EO                                                             115   Ni                                                                               1  H                                                                   5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH                                                                               H  3PO/6EO                                                             116   Ni                                                                               2  tetra-Me                                                            5-OC.sub.6 H.sub.2 (2,6-di-Me)                                                       NH                                                                               H  4PO/3EO                                                             117   Ni                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-OEt)                                                           NH                                                                               H   3BO/10EO                                                           118   Ni                                                                               1  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               H  2PO/8EO                                                             119   Ni                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-OEt)                                                           NH                                                                               H  4PO/3EO                                                             120   Ni                                                                               1  tetra-OEt                                                           3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me  2PO/10EO                                                           121   Ni                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 4PO/3EO                                                             122   Ni                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 2PO/7EO                                                             123   Ni                                                                               2  di-OEt                                                              3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 4PO/3PO                                                             124   Ni                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               Me 3PO/5EO                                                             125   Ni                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H   2PO/10EO                                                           126   Ni                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Cl)                                                            NH                                                                               H  4PO/3EO                                                             127   Ni                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Br)                                                            NH                                                                               H  2PO/7EO                                                             128   Ni                                                                               1  tetra-Cl                                                            4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6PO/3EO                                                             129   Ni                                                                               2  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6BO/6EO                                                             130   Ni                                                                               3  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me  2PO/10EO                                                           131   Ni                                                                               4  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/3EO                                                             132   Ni                                                                               2  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               Me 2PO/4EO                                                             133   Ni                                                                               4  di-OEt                                                              4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  2PO/6EO                                                             134   Ni                                                                               1  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  5PO/5EO                                                             135   Ni                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  4PO/3EO                                                             136   Ni                                                                               3  di-Cl                                                               3-SC.sub. 6 H.sub.3 (4-Me)                                                           NH                                                                               H  3BO/2EO                                                             137   Ni                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/5EO                                                             138   Ni                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 2BO/4EO                                                             139   Ni                                                                               4  tetra-Br                                                            3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               Me 3BO/2EO                                                             140   Co                                                                               1  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2PO/7EO                                                             142   Co                                                                               2  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 6BO/6EO                                                             143   Co                                                                               3  tetra-O-n-C.sub.4 H.sub.9                                           4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me  2PO/10EO                                                           144   Co                                                                               4  H                                                                   4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/3EO                                                             145   Co                                                                               2  di-Br                                                               4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 4PO/3EO                                                             146   Co                                                                               4  tetra-Br                                                            4-OC.sub.6 H.sub.4                                                                   NH                                                                               Me 2BO/4EO                                                             147   Co                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H   2PO/14EO                                                           148   Co                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  4PO/3EO                                                             149   Co                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  2BO/6EO                                                             150   Co                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (2-OMe)                                                            NH                                                                              H  5PO/3EO                                                             151   Co                                                                               2  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H   2PO/10EO                                                           152   Co                                                                               4  H                                                                   5-OC.sub.6 H.sub.3 (2-OMe)                                                           NH                                                                               H  2BO/3EO                                                             153   Co                                                                               1  di-Cl                                                               3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H   2PO/14EO                                                           154   Co                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  4PO/3EO                                                             155   Co                                                                               3  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/8EO                                                             156   Co                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/7EO                                                             157   Co                                                                               2  di-Et                                                               3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/4EO                                                             158   Co                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  12 EO                                                               159   Co                                                                               1  H                                                                   5-OC.sub.6 H.sub.3 (2-Me)                                                            NH                                                                               H  2BO/4EO                                                             160   Co                                                                               1  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               H   2PO/10EO                                                           161   Co                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               H  4PO/3EO                                                             162   Co                                                                               4  tetra-Br                                                            3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               H  2PO/7EO                                                             163   Co                                                                               2  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               H  4PO/3EO                                                             164   Co                                                                               4  H                                                                   3-OC.sub.6 H.sub.3 (4-t-Bu)                                                          NH                                                                               H  3PO/5EO                                                             165   Co                                                                               1  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6PO/3EO                                                             166   Co                                                                               2  di-OMe                                                              4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  6BO/6EO                                                             167   Co                                                                               3  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               H   2PO/10EO                                                           168   Co                                                                               4  H                                                                   4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  2BO/3EO                                                             169   Co                                                                               3  di-Cl                                                               4-SC.sub.6 H.sub.4                                                                   NH                                                                               H  2PO/4EO                                                             170   Co                                                                               1  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  8PO/8EO                                                             171   Co                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  4PO/3EO                                                             172   Co                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-OMe)                                                           NH                                                                               H  2PO/7EO                                                             173   Co                                                                               1  tri-Cl                                                              3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  5PO/5EO                                                             174   Co                                                                               2  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  4PO/3EO                                                             175   Co                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2PO/5EO                                                             176   Co                                                                               2  di-Br                                                               3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  2BO/4EO                                                             177   Co                                                                               4  H                                                                   3-SC.sub.6 H.sub.3 (4-Me)                                                            NH                                                                               H  3BO/2EO                                                             __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR52##                                                                     Exam.                                                                              n [SO.sub.2 N(R.sub.2)Y].sub.1-4                                                                 DZ         N(R.sub.2)                                                                            Y                                      __________________________________________________________________________     1   4 tetra-SO.sub.2 NH4PO/3EO                                                 4-OC.sub.6 H.sub.4               NH     4PO/3EO                                2   4 tetra-SO.sub.2 N(CH.sub.3)2BO/6EO                                        4-OC.sub.6 H.sub.4                                                                 N(CH.sub.3)                                                                      2BO/6EO                                                                  3   4 di-SO.sub.2 N(C.sub.6 H.sub.5)4PO/3EO                                    4-SC.sub.6 H.sub.4                                                                 N(C.sub.6 H.sub.5)                                                                2PO/14EO                                                                4   8 tetra-SO.sub.2 (C.sub.6 H.sub.11)2PO/4EO                                 3-OC.sub.6 H.sub.3 (4-OMe)                                                         NH                                                                               2BO/6EO                                                                  5   8 mono-SO.sub.2 N(C.sub.2 H.sub.5)9PO/1EO                                  4-OC.sub.6 H.sub.4                                                                 N(C.sub.2 H.sub.5)                                                               4PO/3EO                                                                  6   4 tetra-SO.sub.2 N(Y)6PO/6EO                                               4-OC.sub.6 H.sub.4                                                                 N(CH.sub.3)                                                                      2BO/6EO                                                                  7   4 di-SO.sub.2 N(C.sub.6 H.sub.5)4PO/3EO                                    5-OC.sub.6 H.sub.3 (2-OMe)                                                         NH                                                                                2PO/10EO                                                                8   4 tetra-SO.sub.2 NH2PO/4EO                                                 3-OC.sub.6 H.sub.3 (4-OMe)                                                         N(Y)                                                                             9PO/1EO                                                                  9   8 di-SO.sub.2 NH4PO/3EO                                                    3-OC.sub.6 H.sub.3 (4-Cl)                                                          NH                                                                               4PO/3EO                                                                  10  4 tetra-SO.sub.2 NH2BO/6EO                                                 4-OC.sub.6 H.sub.4                                                                 NH                                                                               2BO/6EO                                                                  11  4 tetra-SO.sub.2 NH4PO/3EO                                                 3-SC.sub.6 H.sub.3 (4-OEt)                                                         NH                                                                               4PO/3EO                                                                  12  8 tetra-SO.sub.2 NH2BO/3EO                                                 3-C.sub.6 H.sub.3 (4-OMe)                                                          NH                                                                               2BO/6EO                                                                  13  8 di-SO.sub.2 NH9PO/1EO                                                    4-OC.sub.6 H.sub.4                                                                 NH                                                                               5 PO                                                                     14  4 di-SO.sub.2 NH6PO/8EO                                                    4-OC.sub.6 H.sub.4                                                                 NH                                                                                2PO/10EO                                                                15  8 di-SO.sub.2 NH4PO/3EO                                                    5-OC.sub.6 H.sub.3 (2-OEt)                                                         NH                                                                                2PO/14EO                                                                16  4 di-SO.sub.2 NH2PO/4EO                                                    3-OC.sub.6 H.sub.3 (4-OMe)                                                         NH                                                                               8PO/2EO                                                                  __________________________________________________________________________ 

We claim:
 1. A colorant having the formula A--[D--Z--SO₂ --N(R₂)--Y]_(n),wherein A is non-ionic phthalocyanine chromophore of Cu, Ni or Al; n is 1-16; wherein R₂ is hydrogen, C1-C20 alkyl or cycloalkyl, phenyl, benzyl or Y; Z is an arylene moiety selected from benzene, naphthalene, anthracene, biphenyl, thiophene, benzothiazole, benzoxazole, furan, thiazole, thiadiazole and quinoline; D is a linking group selected from O, SO₂, S, N(R₃) and N(SO₂ R₄), where R₄ is C1-C20 alkyl or cycloalkyl, and R₃ is hydrogen or R₄ ; Y is a poly(oxyalkylene) moiety comprising at least three monomeric units selected from the formula (--RO--), wherein each R is an alkylene of 2-4 carbons, and Y is terminated with a group selected from hydrogen, C1-C20 alkyl, C1-C20 cycloalkyl, phenyl, and groups having the formula: ##STR53## where R₅ and R₆ are selected from hydrogen, methyl and ethyl.
 2. The colorant of claim 1 where n is 1-4.
 3. The colorant of claim 2 wherein Y has an average molecular weight of from 200 to
 1500. 4. The colorant of claim 3 wherein R₂ is selected from hydrogen, and C1-C6 alkyl or cycloalkyl.
 5. The colorant of claim 4 wherein A is phthalocyanine chromophore of Cu.
 6. The colorant of claim 1 wherein Y has an average molecular weight of from 200 to 1500, and Y is terminated with a group selected from hydrogen, C1-C4 alkyl or a group having the formula: ##STR54## wherein R₅ is selected from hydrogen, methyl and ethyl.
 7. The colorant of claim 6 wherein R₂ is hydrogen and A is phthalocyanine chromophore of Cu.
 8. The colorant of claim 7 wherein D is O and Z is a benzene moiety.
 9. The colorant of claim 7 wherein n is 1-4.
 10. The colorant of claim 2 wherein D is selected from O and S.
 11. The colorant of claim 10 wherein Z is a benzene moiety.
 12. The colorant of claim 11 wherein R₂ is hydrogen.
 13. A colorant having the formula A--[D--Z--SO₂ --N(R₂)--Y]_(n),wherein A is non-ionic phthalocyanine chromophore of Cu, Ni or Al; n is 1-16; wherein R₂ is hydrogen, C1-C20 alkyl or cycloalkyl, phenyl, benzyl or Y; Z is an arylene moiety selected from benzene, naphthalene, anthracene, biphenyl, thiophene, benzothiazole, benzoxazole, furan, thiazole, thiadiazole and quinoline; D is a linking group selected from O, SO₂, S, N(R₃) and N(SO₂ R₄), where R₄ is C1-C20 alkyl or cycloalkyl, and R₃ is hydrogen or R₄ ; Y is a poly(oxyalkylene) moiety comprising at least three monomeric units selected from the formula (--RO--), wherein each R is an alkylene of 2-4 carbons, and Y is terminated with a group selected from hydrogen, C1-C20 alkyl, C1-C20 cycloalkyl, C1-C20 acyl, phenyl, and groups having the formula: ##STR55## where R₅ and R₆ are selected from hydrogen, methyl and ethyl. 